WO2000015898A1

WO2000015898A1 - Method for printing fibrous textile materials according to the ink jet method

Info

Publication number: WO2000015898A1
Application number: PCT/EP1999/006480
Authority: WO
Inventors: Hanspeter Hermann
Original assignee: Ciba Specialty Chemicals Holding Inc.
Priority date: 1998-09-16
Filing date: 1999-09-03
Publication date: 2000-03-23
Also published as: AU5859499A

Abstract

The invention relates to a method for printing fibrous textile materials according to the ink jet method. The inventive method is characterised in that each mixed colour of a textile print is produced with one aqueous ink of the corresponding mixed colour, the mixed colour shade of the inks being determined by mixing at least two reactive, acidic, disperse or pigment dyes of different colours in the appropriate quantities for the desired mixed colour shade. According to the inventive method, any mixed colour shade, even the finest tints, can be produced on the fibrous material and all of the mixed colours of the printed fabric will appear homogenous to the observer.

Description

Process for printing textile fiber materials according to the inkjet printing process

The present invention relates to a method for printing textile fiber materials using the inkjet printing method.

Inkjet printing processes have been used in the textile industry for several years. These methods make it possible to dispense with the otherwise customary production of a printing stencil, so that considerable cost and time savings can be achieved. In particular in the production of sample templates, it is possible to react to changing needs within a significantly shorter time.

Until now, however, it has been customary in these ink jet printing processes to produce mixed colors on the fiber material to be printed by means of the so-called digital mixing of the basic colors usually used in ink jet printing, such as yellow, red, turquoise and black. For this purpose, the number of ink droplets of the corresponding primary colors required for the mixed color to be produced are metered side by side onto a unit area of the material to be printed in such a way that the viewer receives the sensory impression of the desired mixed color from a certain distance. This principle is also the basis for the way a color television set works, or the painting style used by the pointilists Seurat or Signac. The viewer's sensation is naturally dependent on the size of the color points. In the case of deep or intensive mixed color tones, a unit area of the fiber material to be printed is almost completely covered with color dots of the corresponding primary colors. In contrast, in light or less intensive mixed color tones, an area unit of the textile material under consideration is only partially covered with color dots. Digital mixing from the primary colors comes up against its physical limits, particularly in the case of the less intensive mixed color tones, since the eye, even if the printed material is viewed from a certain distance, can resolve the individual color dots and perceives them separately. For this reason, the colors of the printed fiber material appear inhomogeneous to the viewer, which is not desirable in textile printing because it does not meet the needs of the consumers. On the other hand, in textile printing it is desirable in many cases that the color on both sides of the "printed material" has the same intensity and thus, for example, a color design consisting of several colors appears to the viewer's eye on both sides with the same color intensity. However, this is only guaranteed , if the ink, which is usually applied on one side, migrates through the material to be printed and the side of the fiber material facing away from the ink jet head is also wetted by the ink, in particular the light or less intensive mixed color tones, in which a unit area of the In this regard, fiber material is only partially covered with ink drops, since the concentration of the applied ink is too low to migrate through the material to be printed, so that the viewer only sees the intense colors on both sides of the textile material in the same color intensity , while the less intense colors on the unprinted side appear pale and pale to the eye of the beholder.

The known processes do not meet all of the above requirements in all properties, so that there is a need for new processes for textile inkjet printing which do not have the disadvantages mentioned.

The present invention thus relates to a process for printing textile fiber materials by the inkjet printing process, characterized in that each mixed color of a textile print is produced with in each case an aqueous ink of the corresponding mixed color, the mixed color of the inks being obtained by mixing at least two reactive , Acid, dispersion or pigment dyes of different colors in the amount required for the desired mixed color.

The term mixed color in connection with the present subject matter of the invention is to be understood as those colors which do not correspond to the basic colors usually used in the ink jet printing of textile fiber materials, such as yellow, red, turquoise and black. In the usual ink jet printing processes used in the textile industry, the mixed colors are first generated by digital color mixing from the primary colors on the fiber material to be printed. The inks of the primary colors usually contain only one dye. The method according to the invention is preferably carried out in such a way that the ink applied to the fiber material covers the surface of the fiber material in such a way that it migrates through the fiber material, so that the side of the fiber material facing away from the ink-jet head is also colored.

The inks used in the process according to the invention contain at least two dyes of different colors from the class of reactive dyes or at least two dyes of different colors from the class of acid dyes or at least two dyes of different colors from the class of disperse dyes or at least two pigments of different colors, i.e. only dyes of the same dye class are mixed with one another to produce the inks for the process according to the invention.

The reactive dyes are e.g. to dyes from the group of the monoazo, disazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine dyes which contain at least one reactive group. These dyes preferably also contain at least one sulfo group.

Reactive groups are radicals which are reactive to fibers and are capable of reacting with the hydroxyl groups of cellulose, the amino, carboxyl, hydroxyl and mercapto groups of wool or silk or with the amino or, if appropriate, the carboxyl groups of synthetic polyamides to form chemical to react covalent bonds. The reactive groups are usually linked to the dye residue directly or via a bridge element. As reactive groups e.g. suitable are those which have at least one substituent which can be removed from an aliphatic, aromatic or heterocyclic radical, or those in which these radicals have a radical which is suitable for reaction with the fiber material, such as e.g. a halotriazinyl, halopyrimidinyl or vinyl radical.

As aliphatic reactive groups there are e.g. those of the following formulas:

-NH-CO-Y (1),

-S0 ₂ -Z (1a), W - alkylene - - S0 ₂ -Z

(1 b),

R

-W- alkylene - ^• E alkylene '- S0 ₂ -Z (1 C),

-alkylene— W - alkylene'— S0 ₂ -Z

(1d), R

-O- alkylene- W - alkylene'— S0 ₂ -Z

(1e), R

-W - arylene-N - alkylene - S0 ₂ -Z i R ₁ i R < ^1f >'wherein

W is a group of the formula -S0 ₂ -NR _r , -CONR _r or -NR1CO-,

Ri is hydrogen, unsubstituted or substituted by hydroxy, sulfo, sulfato, carboxy or cyano, C _r C -alkyl or a radical of the formula -alkylene— S0 ₂ -Z _

R

R is hydrogen, hydroxy, sulfo, sulfato, carboxy, cyano, halogen, CC ₄ alkoxycarbonyl,

CrCrAlkanoyloxy, Carbamoyi or the group -S0 ₂ -Z,

Z vinyl or a rest

is a leaving group,

Y is a radical of the formula -CH (Hal) -CH ₂ -Hal or -C (Hal) = CH ₂ and Hai halogen,

E is the radical -O- or -N (R ₂ ) -,

R _{2 is} hydrogen or C rCj-alkyl, alkylene and alkylene 'independently of one another d-Ce-alkylene, and arylene an unsubstituted or by sulfo, carboxy, CC-alkyl, CrC ^ alkoxy or

Halogen substituted phenylene or naphthylene means. As the aliphatic reactive groups are those of the formulas (1a) to (1d), in particular such ^"the formulas (1a) to (1c), and preferably those of the formula (1a) are preferred.

Preferred heterocyclic reactive radicals are 1,3,5-triazine radicals of the formula

M.

-N- ^• V

R, N, N (2)

X

considering where

R _{3 is} hydrogen or unsubstituted or by carboxy, cyano, hydroxy, sulfo or

Sulfato substituted CC ₄ alkyl,

X is a group which can be split off as an anion and

V is a radical of the formula

R

-N- alkylene S0 ₂ -Z (3a),

R,

^• alkylene - E - alkylene'-S0 ₂ -Z

(3b),

R,

^• N arylene S0 ₂ -Z

(3c),

R-,

- - arylene - (alkylene) - W alkylene '- S0 ₂ -Z

(3d),

R ₃ NN alkylene - S0 ₂ -Z (3e) or

-N— arylene -NH-CO-Y

(3f) R,

means what

R, RR ₃ , E, W, Z, Y, alkylene, alkylene 'and arylene have the meanings given above and 1 is 0 or 1.

The leaving group U _Ϊ is, for example, -Cl, -Br, -F, -OSO ₃ H, -SS0 ₃ H, -OCO-CH3, -OPO3H2, -OCO-C ₆ H ₅ , -OSO ₂ -Cι -C ₄ alkyl or -OSO ₂ -N (C ₁ -C ₄ alkyl) ₂ . U ₁ is preferably a group of the formula -Cl, -OS0 ₃ H, -SS0 ₃ H, -OCO-CH ₃ , -OCO-C ₆ H ₅ or -OPO ₃ H ₂ , in particular -Cl or -OS0 ₃ H and particularly preferred -OSO ₃ H.

Alkylene and alkylene 'are independently of each other e.g. a methylene, ethylene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene or 1, 6-hexylene radical or their branched isomers.

Alkylene and alkylene 'preferably represent a CC ₄ alkylene radical and particularly preferably an ethylene radical.

R is preferably hydrogen or the group -S0 ₂ -Z, where Z has the meanings and preferences given above. R particularly preferably represents hydrogen.

Ri is preferably hydrogen, CC ₄ -alkyl or a group -alkylene-SO ₂ -Z, where alkylene and Z each have the meanings given above. R ^ is particularly preferably hydrogen or CC ₄ alkyl, in particular hydrogen.

R ₃ is preferably hydrogen or a dC -alkyl radical and particularly preferably hydrogen. Arylene is preferably a 1,3- or 1,4-phenylene radical which is unsubstituted or substituted, for example, by sulfo, methyl, methoxy or carboxy.

E preferably represents -NH- and particularly preferably -O-.

W preferably denotes a group of the formula -NHCO- or in particular -CONH-.

X represents, for example fluorine, chlorine, bromine, sulfo, C _r C ₄ alkylsulfonyl or phenylsulfonyl and preferably chlorine or especially fluorine.

Shark is preferably chlorine or bromine, especially bromine.

Other interesting reactive groups are those of the formula (2), in which V is a group which can be split off as an anion or in particular denotes a non-reactive substituent.

If V is a group which can be split off as an anion, this is, for example, fluorine, chlorine, bromine, sulfo, CrC ₄ -alkylsulfonyl or phenylsulfonyl and preferably chlorine or in particular fluorine.

V stands for a non-reactive substituent, this can be, for example, a hydroxy, CC alkoxy, CrCrAlkylthio, amino, N-CrC ^ alkylamino or N, N-di-C 1 -C ₄ alkylamino, where the alkyl is optionally substituted, for example, by sulfo, sulfato, hydroxyl, hydroxyethoxy, carboxy or phenyl, cyclohexylamino, morpholino, or N-CrC ^ alkyl-N-phenylamino or phenylamino or naphthylamino radical, the phenyl or naphthyl optionally being, for example, by dC -alkyl, CC -alkoxy, carboxy, sulfo or halogen is substituted.

Examples of suitable non-reactive substituents V are amino, methylamino, ethylamino, ß-hydroxyethylamino, N, N-di-ß-hydroxyethylamino, ß-sulfoethylamino, cyclohexylamino, morpholino, o-, m- or p-chlorophenylamino, o-, m- or p-methylphenylamino, o-, m- or p-methoxyphenylamino, o-, m- or p-sulfophenylamino, disulfophenylamino, o- carboxyphenylamino, 1- or 2-naphthylamino, 1-sulfo-2-naphthylamino, 4, 8-disulfo-2- naphthylamino, N-ethyl-N-phenylamino, N-methyl-N-phenylamino, methoxy, ethoxy, n- or ^" iso-propoxy and hydroxy.

As a non-reactive substituent, V preferably has the meaning amino, NC C ₄ -alkylamino, which is unsubstituted in the alkyl part or substituted by hydroxy, hydroxyethoxy, sulfato or sulfo, morpholino, phenylamino or NC d-alkyl-N-phenylamino, in which the phenyl is in each case unsubstituted or substituted by sulfo, carboxy, methyl or methoxy. Particularly preferred are the meanings as N-CrC ₄ -alkylamino, which is unsubstituted in the alkyl part or substituted by hydroxy, hydroxyethoxy, sulfato or sulfo, and as phenylamino or Ndd-alkyl-N-phenylamino, in which the phenyi is in each case unsubstituted or by sulfo, Carboxy, methyl or methoxy is substituted.

Preferred residues of the formulas (3a) to (3f) here and below are those of the formulas (3a) to (3d), in particular those of the formulas (3b) and (3d).

Preferred heterocyclic reactive radicals of the formula (2) are those in which X is fluorine or chlorine, in particular fluorine, and V represents a radical of the formulas (3a) to (3f).

Also preferred are reactive radicals of the formula (2) in which X is fluorine or chlorine, in particular chlorine, and V is amino, NdC ₄ -alkylamino substituted by hydroxyethoxy in the alkyl part, or optionally by dC -alkyl, CC -alkoxy, carboxy, halogen or in particular Sulfo substituted phenylamino or N-CrC-alkyl-N-phenylamino. The phenyl radicals are preferably unsubstituted or substituted by sulfo. Of particular importance here are amino and phenylamino or NdC -alkyl-N-phenylamino which is unsubstituted or substituted by sulfo in the phenyl radical.

Also of interest as heterocyclic reactive radicals are those of the formula

wherein one of the radicals Xi is a group which can be split off as an anion and the other radical X has the meanings and preferences given for V as non-reactive substituents or is a radical of the formulas (3a) to (3f) or a group which can be split off as an anion,

X _{2 is} a negative substituent and

R ₃ independently has the meaning given above.

The radical Xi which can be split off as an anion is preferably chlorine or in particular fluorine. Examples of suitable radicals X ₂ are nitro, cyano, CC ₄ alkylsulfonyl, carboxy, chlorine, hydroxy, dC -alkoxysulfonyl, dC ₄ -alkylsulfinyl, C _r C ₄ -alkoxycarbonyl or C ₂ -C -alkanoyl, the meanings being chlorine, Cyano and methylsulfonyl, especially chlorine, are preferred for X ₂ . At least one of the radicals X is particularly preferably fluorine or a radical of the formulas (3a) to (3f). One of the radicals X 1 is very particularly preferably fluorine and the other radical X is fluorine or chlorine, X ₂ having the meanings and preferences given above.

Reactive groups of the formula (1a) or (2) are of particular interest, the stated preferences applying.

In addition to the reactive groups, the reactive dyes can contain the substituents customary in organic dyes bound to their backbone.

Examples of such substituents for the reactive dyes are: alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl or butyl, where the alkyl radicals can be further substituted, for example by hydroxyl, sulfo or sulfato; Alkoxy groups with 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, it being possible for the alkyl radicals to be further substituted, for example by hydroxyl, sulfo or sulfato; phenyl optionally substituted by dC ₄ alkyl, dC ₄ alkoxy, halogen, carboxy or sulfo; Acylamino groups with 1 to 8 carbon atoms, especially those alkanoylamino groups such as acetylamino or propionylamino; benzoylamino optionally substituted in the phenyl ring by C _r C ₄ alkyl, CC ₄ alkoxy, halogen or sulfo; phenylamino optionally substituted in the phenyl ring by dC ₄ alkyl, dC ₄ alkoxy, halogen or sulfo; N, N-di-ß-hydroxyethylamino; N, N-Di-ß-sulfatoethylamino; Sulfobenzylamino; N, N-disulfobenzylamino; Alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, such as methoxycarbonyl or ethoxycarbonyl; Alkylsulfonyl with 1 to 4 Carbon atoms such as methylsulfonyl or ethylsulfonyl; Trifluoromethyl; Nitro; Amino; Cyano; Halogen such as fluorine, chlorine or bromine; Carbamoyl; N-alkylcarbamoyl with 1 to 4 carbon atoms in the alkyl radical, such as N-methylcarbamoyl or N-ethylcarbamoyl; Sulfamoyl; N-mono- or N, N-dialkylsulfamoyl each having 1 to 4 carbon atoms, such as N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl or N-butylsulfamoyl, it being possible for the alkyl radicals to be further substituted, for example by hydroxyl or sulfo; N- (β-hydroxyethyl) sulfamoyl; N, N-di- (β-hydroxyethyl) sulfamoyl; N-phenylsulfamoyl optionally substituted by CC ₄ alkyl, CC ₄ alkoxy, halogen, carboxy or sulfo; Ureido; Hydroxy; Carboxy; Sulfomethyl or sulfo. The reactive dyes preferably contain at least one sulfo or sulfato group, in particular 1 to 6 such groups and preferably 2 to 6 such groups.

Examples of reactive dyes are those of the formula

A, -U (5)

considering where

Ai is the remainder of a monoazo, disazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine dye and U is a reactive radical, the meanings and preferences given above especially for the reactive radicals U here and below. The radical A ^ may also contain one or more further, identical or different, reactive groups U. The total number of reactive groups in the dyes is preferably 1 to 3, preferably 1 or 2 and in particular 2. U is preferably a reactive radical of the above formula (1a) or (2).

Further reactive dyes are, for example those of the formula

x; X ₂ '

considering where R. R _δ> Re and R ₇ independently of one another are hydrogen or optionally substituted ^“ dC ₄ -alkyl,

Xi 'and X ₂ ' are halogen,

B is an aromatic or aliphatic bridge member or the rest of the formula

-N (R ₅ ) -B ₁ -N (R ₆ ) - represents a piperazine residue, and

A ₂ and A ₃ independently of one another have the meanings given above for A ^.

The radicals R ₄ , R ₅ , R ₆ and R ₇ are straight-chain or branched as alkyl radicals. The alkyl radicals can be further substituted, for example by hydroxy, sulfo, sulfato, cyano or carboxy. The following radicals may be mentioned as examples: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, and the corresponding radicals substituted by hydroxyl, sulfo, sulfato, cyano or carboxy. Hydroxy, sulfo or sulfato, in particular hydroxy or sulfato and preferably hydroxy, are preferred as substituents.

R, R ₅ , R ₆ and R ₇ are preferably hydrogen or CC ₄ alkyl, in particular hydrogen.

X ^ and X ₂ 'are preferably independently chlorine or fluorine, especially fluorine.

As an aliphatic bridge member, B ^ is, for example, a C ₂ -C ₁₂ alkylene radical, in particular a C ₂ -C ₆ alkylene radical, which has 1, 2 or 3 members from the group -NH-, -N (CH ₃ ) - or in particular -O- can be interrupted and is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or carboxy. Hydroxy, sulfo or sulfato, in particular hydroxy, are preferred as substituents of the alkylene radicals mentioned for B ^.

Other suitable aliphatic bridge members for B _t are, for example, C ₅ -C ₉ cycloalkylene radicals, such as, in particular, cyclohexylene radicals. The cycloalkylene radicals mentioned can optionally be substituted by dC -alkyl, dC -alkoxy, C ₂ -C ₄ -alkanoylamino, sulfo, halogen or carboxy, in particular by CC -alkyl. As aliphatic bridging elements, methylene-cyclohexylene-methylene radicals optionally substituted in the cyclohexylene ring by dC ₄ -alkyl may also be mentioned for B. For the rest of the formula -N (R ₅ ) -BrN (R ₆ ) - a piperazine radical is, for example, a radical of the formula

-N N - m consideration. \ /

As an aromatic bridge member, B ^ is, for example, dC ₆ -alkylenephenylene or phenylene or a radical of the formula which is optionally substituted by dd-alkyl, CC-alkoxy, C ₂ -C -alkanoylamino, sulfo, halogen or carboxy

wherein the benzene rings I and II are optionally substituted by CC ₄ alkyl, dC alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or carboxy and L is the direct bond or a C ₂ -C ₀ alkylene radical, which by 1, 2 or 3 oxygen atoms can be interrupted, or L is a bridge member of the formula -CH = CH-, -N = N-, -NH-, -CO-, -NH-CO-, -NH-CO-NH-, -O-, -S- or -S0 ₂ - is. As an aromatic bridge member, B is preferably phenylene, which can be substituted as indicated above. The aromatic bridge members mentioned for B ^ are preferably unsubstituted or substituted by sulfo.

Preferred is a C ₂ -C ₂ alkylene radical which has 1, 2 or 3 members from the group

-NH-, -N (CH ₃ ) - or -O- can be interrupted and unsubstituted or by hydroxy,

Sulfo, sulfato, cyano or carboxy is substituted; or a C ₅ -C ₉ cycloalkylene radical, dC ₆ alkylenephenylene radical or optionally substituted by dC-alkyl, CC ₄ -alkoxy, C ₂ -C ₄ -alkanoylamino, sulfo, halogen or carboxy

Phenylene radical; or Bi is a radical of the formula (7), in which the benzene rings I and II are optionally substituted by dC-alkyl, dC ₄ -alkoxy, C ₂ -C ₄ -alkanoylamino, sulfo, halogen or carboxy and L is the direct bond or a C ₂ -C ₁₀ alkylene radical which is represented by 1, 2 or 3

Oxygen atoms can be interrupted, or L is a bridge member of the formula -CH = CH-,

-N = N-, -NH-, -CO-, -NH-CO-, -NH-CO-NH-, -O-, -S- or -S0 ₂ -; or the radical of the formula -N (R ₅ ) -B ₁ -N (R ₆ ) - is a piperazine radical of the formula

- N N—.

B is particularly preferably a C ₂ -C ₁₂ alkylene radical which can be interrupted by 1, 2 or 3 members -O- and is unsubstituted or substituted by hydroxyl, sulfo, sulfato, cyano or carboxy, or one optionally substituted by dC ₄ - Alkyl, dC ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or carboxy substituted phenylene radical.

B ^ is very particularly preferably a C ₂ -C ₂ alkylene radical, in particular a C ₂ -C ₆ alkylene radical, which can be interrupted by 1, 2 or 3 members -O- and is unsubstituted or substituted by hydroxy.

Of particular importance as B ^ radicals are C ₂ -C ₆ alkylene radicals, in particular 1,3-propylene and 1,2-ethylene.

Of particular interest as reactive dyes of the formula (6) are those in which X and X ₂ 'are fluorine.

The following are preferably suitable as monoazo, polyazo or metal complex azo dye residues for A ^ A ₂ and A ₃ :

Mono- or disazo dye residues of the formula

DN = N- (MN = N) _U -K- (8) or

-DN = N- (MN = N) _U -K (9),

wherein D is the remainder of a diazo component of the benzene or naphthalene series, M is the remainder of a middle component of the benzene or naphthalene series, K is the remainder of a coupling component of the benzene, naphthalene, pyrazolone, 6-hydroxypyridone (2) or acetoacetic acid arylamide series and u is the number 0 or 1, where D, M and K are customary substituents in azo dyes, for example optionally by hydroxy, sulfo or sulfato further substituted C _r C ₄ alkyl or CC ₄ alkoxy, halogen, carboxy, sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, amino, ureido, hydroxy, carboxy, sulfomethyl, C ₂ -C ₄ alkanoylamino, optionally in the phenyl ring benzoylamino substituted by C _r C ₄ alkyl, CC ₄ alkoxy, halogen or sulfo, optionally substituted by CC alkyl, dC ₄ alkoxy, halogen, carboxy or sulfo, and fiber-reactive radicals. Furthermore, the metal complexes derived from the dyes of the formulas (8) and (9) also come into consideration, these being in particular 1: 1 copper complex azo dyes of the benzene or naphthalene series, in which the copper atom is attached to a metallizable group, such as, for example, a Hydroxy group, bound on both sides in the ortho position to the azo bridge. If the dye radicals of the formula (8) or (9) carry a reactive radical, the meanings and preferences given above apply to them.

The dye residues of the formulas (8) and (9) are preferably those of the formulas

wherein

(R ₈ ) ₀ - ₃ for 0 to 3 identical or different substituents from the group dC ₄ -alkyl, dC ₄ -alkoxy, C ₂ -C ₄ -alkanoylamino, ureido, sulfamoyl, carbamoyl, sulfomethyl,

Halogen, nitro, cyan, trifluoromethyl, amino, hydroxy, carboxy and sulfo,

(R ₉ ) o- ₂ for 0 to 2 identical or different substituents from the group hydroxyl, amino,

N-mono-dC ₄ alkylamino, N, N-di-dC ₄ alkylamino, C ₂ -C ₄ alkanoylamino and

Benzoylamino stands and

(U) _{_0-2} is 0 to 2 identical or different reactive groups;

wherein

(R ₉₎ o- (U) ₀ ₂ and - ₂ have the meanings given above;

wherein

(Rιo) o- ₃ and (Ru) o- ₃ independently of one another represent 0 to 3 identical or different substituents from the group dC ₄ -alkyl, dC ₄ -alkoxy, halogen, carboxy and sulfo and (U) ₀ - ₂ are has the meanings given above;

wherein

R ₁₂ and R _{14 are} independently hydrogen, CC ₄ alkyl or phenyl, and R _{3 is} hydrogen, cyano, carbamoyl or sulfomethyl;

wherein

(Rιe) o- _{3 is} 0 to 3 identical or different substituents from the group dC ₄ alkyl, CC ₄ alkoxy, halogen, amino, carboxy and sulfo,

(R ₁₅ ) o- ₃ and (Rι ₇ ) o- ₃ independently of one another have the meanings given above for (R ₈ ) ₀ - ₃ , and

(U) o- _{2 has} the meanings given above;

(

wherein

(Ri5) o- _3> (i7) o- ₃ and (U) ₀ - _{2 have} the meanings given above and

(Rιβ) o- ₂ for 0 to 2 identical or different substituents from the group dC ₄ alkyl, dC alkoxy, halogen, carboxy, sulfo, hydroxy, amino, N-mono-C C -alkylamino,

N, N-Di-dC -alkylamino, C ₂ -C ₄ -alkanoylamino and benzoylamino.

The remainder of a formazan dye for A ^ A ₂ and A _{3 are,} for example, those of the formula

considering where

(U) o- _{2 has} the meanings given above and the benzene nuclei contain no further substituents or are further substituted by C _r C -alkyl, CC ₄ -alkoxy, dC -alkylsulfonyl, halogen or carboxy.

The remainder of a phthalocyanine dye for A ^ A ₂ and A _{3 are,} for example, those of the formula

(S0 ₂ W)

Pc.

\

S0 ₂ -NA- (12)

'19

considering where

Pc the rest of a metal phthalocyanine, especially the rest of a copper or

Nickel phthalocyanine, is

W -OH and / or -NR ₂₀ R ₂₀ ',

R ₂₀ and R ₂₀ 'independently of one another are hydrogen or optionally by hydroxy or

Sulfo substituted C _r C ₄ alkyl,

R _{19 is} hydrogen or dd-alkyl,

A is optionally substituted by d-C alkyl, halogen, carboxy or sulfo

Phenylene radical or a C ₂ -C ₆ alkylene radical and k is 1 to 3. The remainder of a dioxazine dye for Ai, A ₂ and A _{3 are,} for example, those of the formula

H

considering where

A 'an optionally substituted by C C alkyl, halogen, carboxy or sulfo

Phenylene radical or a C ₂ -C ₆ alkylene radical, r, s, v and v 'independently of one another each represent the number 0 or 1 and

Z has the meaning given above.

The rest of an anthraquinone dye for A, A and A _{3 are,} for example, those of the formula

considering where

G is an unsubstituted or substituted by dC ₄ alkyl, dC alkoxy, halogen, carboxy or sulfo phenylene radical or a cyclohexylene, phenylene methylene or dC ₆ alkylene radical.

The above dye residues of the formulas (10a) to (10f) and (11) to (14) each preferably contain at least one sulfo group, in particular 1 to 4 sulfo groups and preferably 1 to 3 sulfo groups.

The above-mentioned reactive residues are particularly suitable as reactive residues U, the above preferences applying. Preferred are dye residues of the formulas (10a) to (10f), (12) and (14), in particular of the formulas (10a) to (10f) and (14) and preferably those of the formulas (10a) to (10f).

Reactive dyes of the formula are of particular importance

Cl

1: 2 Cr complex

wherein

Z and Z 'are independently vinyl or a radical of the formula -CH ₂ -CH ₂ -OS0 ₃ H, B _t and B _{2 are} a C ₂ -C ₆ alkylene radical, in particular 1,3-propylene or 1,2-ethylene mean, and CuPhC is a copper phthalocyanine residue. B, 1, 3-propylene and B ₂ 1, 2-ethylene are preferred. Z is preferably vinyl and Z 'is the meaning of the radical of the formula -CH ₂ -CH ₂ -OS0 ₃ H preferred.

Suitable disperse dyes for the process according to the invention are e.g. those dyes which are described in the Color Index, 3rd edition (3rd revision 1987 including additions and amendments to No. 85) under "Disperse Dyes". Examples include nitro, amino, amino ketone, ketoninim, methine, polymethine, diphenylamine, quinoline, benzimidazole, xanthene, oxazine or coumarin dyes, and in particular anthraquinone and azo dyes, free of carboxylic acid and / or sulfonic acid groups. such as mono- or disazo dyes.

A preferred group a) of the disperse dyes are dyes of the formula

wherein

R ₂₁ halogen, nitro or cyano,

R _{22 is} hydrogen, halogen, nitro or cyano,

R ₂₃ halogen or cyano,

R _{2 is} hydrogen, halogen, CC ₄ alkyl or dC alkoxy,

R _{25 is} hydrogen, halogen or acylamino, and

R ₂₆ and R ₂₇ are mutually independent allyl, dC ₄ alkyl, which is unsubstituted or by

Hydroxy, acetoxy, dC ₄ -alkoxycarbonyl or phenoxy is substituted, or of the formula

wherein

R _{28 is} hydrogen, phenyl or phenylsulfoxy, the benzene ring in the phenyl and

Phenylsulfoxy is optionally substituted by dC -alkyl or -CC ₄ -alkylsulfo, R ₂₉ amino or hydroxy,

R _{30 is} hydrogen or CC ₄ alkoxy,

R _{31 is} hydrogen or the radical -0-C ₆ H5-S0 ₂ -NH- (CH ₂ ) ₃ -0-C ₂ H ₅ ,

R _{32 is} hydrogen, hydroxy or nitro and

R _{33 is} hydrogen, hydroxy or nitro, or of the formula

wherein

R ₃ CC alkyl which is unsubstituted or substituted by hydroxy,

R ₃₅ dC ₄ alkyl,

R ₃₆ cyano,

R _{37 is} the rest of the formula - (CH ₂ ) ₃ -0- (CH ₂ ) ₂ -0-C ₆ H5,

R ₃₈ halogen, nitro or cyano, and

R _{39 is} hydrogen, halogen, nitro or cyano, or the formula

wherein

R ₀ dC ₄ alkyl,

R ₄₁ CrC ₄ alkyl which is unsubstituted or substituted by -CC alkoxy and

R ₄₂ the residue -COOCHgCHjO _ä Hs and R ₄₃ hydrogen or

R _{42 is} hydrogen and R ₃ -N = NC ₆ H ₅ , or of the formula

wherein the rings A "and B" are unsubstituted or substituted one or more times with halogen, or of the formula

wherein

R, _H dC ₄ alkyl which is unsubstituted or substituted by hydroxy, dC ₄ alkoxy or C ₁ -C ₄ alkoxy-C ₁ -C alkoxy, or of the formula

Dyes of group a) are particularly preferred as dyes of the formulas in the process according to the invention

(23d),

used.

Another group b) of preferred disperse dyes are dyes of the formula

wherein

R _{5 is} hydrogen or phenyl optionally substituted by C _r C ₄ alkyl,

R _{46 is} hydroxy or amino optionally substituted by dC ₄ alkyl, and

R _{47 is} hydrogen, C _r C ₄ alkoxy or phenoxy, or of the formula

wherein

R ₄₈ and R _{49 are} CC alkyl,

R ₅₀ halogen or dC ₄ alkoxy, and

R _{5 is} hydrogen, nitro or halogen, or of the formula

Interesting dyes of this group b) are the dyes of the formulas

Suitable pigment dyes for the process according to the invention are in particular organic pigments, preferably those of phthalocyanine, anthraquinone, perinone, indigo, thioindigoid, dioxazine, diketopyrrolopyrrole, isoindolinone, perylene, azo, quinacridone and Metal complex series, for example metal complexes from azo. Azomethine or methine dyes, as well as classic azo dyes from the β-oxynaphthoic acid and acetoacetarylide series or metal salts of azo dyes. Examples of such pigment dyes are listed in the Color Index, 3rd edition (3rd revision 1987 including additions and amendments to No. 85) under "Pigments". Pigment dyes of the monoazo, disazo, phthalocyanine and anthraquinone series are of particular interest.

Particularly preferred pigment dyes are dyes of the formula

wherein

R _{52 is} hydrogen, halogen, C C-alkyl, C _r C ₄ alkoxy, nitro or cyano,

R _{53 is} hydrogen, halogen, nitro or cyano,

R _{M is} hydrogen, halogen or phenyla inocarbonyl,

R _{55 is} hydrogen or hydroxy, and

Rς _{fi is} hydrogen or a radical of the formula, wherein

R _{57 is} hydrogen, C _r C-alkyl or C C-alkoxy,

R _{58 is} hydrogen, C _r C ₄ alkoxy or halogen, and

R _{59 is} hydrogen, CC alkyl, CC alkoxy or halogen, or of the formula

wherein

R ₆ o and R ₆ ι are independently CC ₄ alkyl and R ₆₂ and R _{63 are} halogen, or the formula

wherein the rings A, B, D and E are unsubstituted or substituted one or more times with halogen, or of the formula

wherein

R _M dd alkyl,

R _{65 is} hydrogen, halogen, dd-alkyl, C _r C ₄ alkoxy, nitro or cyano,

R _{66 is} hydrogen, halogen, nitro or cyano,

R _{67 are} hydrogen, halogen, dC ₄ alkyl, CC alkoxy, nitro or cyano, or of the formula

wherein the rings A 'and B' are unsubstituted or substituted one or more times with halogen. n The dyes of the formulas are of particular interest as pigment dyes

Disperse dyes or pigment dyes, in particular dispersion dyes of groups a) and b), preferably those of group b), are preferably used in the process according to the invention. The pigment dyes are also preferred.

The reactive dyes, disperse dyes and pigment dyes mentioned are known or can be obtained in analogy to known production processes, such as diazotization, coupling, addition and condensation reactions.

Suitable acid dyes for the process according to the invention are, for example, those dyes which are described in the Color Index, 3rd edition (3rd revision 1987 including additions and amendments to No. 85) under "Acid Dyes". The anionic dyes that can be used can belong to a wide variety of dye classes and, if appropriate, contain one or more sulfonic acid groups. These are, for example, triphenylmethane dyes with at least two sulfonic acid groups, heavy metal-free monoazo and disazo dyes each with one or more sulfonic acid groups and heavy metal-containing monoazo, disazo, azomethine and formazan dyes containing copper, chromium, nickel or cobalt, in particular metallized dyes which contain two molecules of azo dye or one molecule of azo dye and one molecule of azomethine dye bound to a metal atom, especially those which contain mono- and / or disazo dyes and / or azomethine dyes as ligands and a chromium or cobalt ion as the central atom, and also anthraquinone dyes , in particular 1-amino-4-arylaminoanthraquinone-2-sulfonic acids or 1, 4-diarylamino or 1-cycloalkylamino-4-arylaminoanthraquinone sulfonic acids. Examples of suitable anionic acid dyes are:

a) Thphenylmethane dyes of the formula

wherein

R ₇₁ , R7 ₂ , R ₇₃ and R _{74 are} independently C _r C ₄ alkyl and R ₇₅ CC ₄ alkyl, CC ₄ alkoxy or hydrogen;

b) mono- and disazo dyes of the formulas

wherein

R _{76 is} benzoylamino, phenoxy, chlorophenoxy, dichlorophenoxy or methylphenoxy, F is hydrogen, benzoyl, phenyl, dd-alkyl, phenylsulfonyl, methylphenylsulfonyl, and the substituents R _{78 are} independently hydrogen or a phenylamino or N-phenyl-N-methylaminosulfonyl;

wherein the phenyl ring B ₁₀ can be substituted by halogen, dC-alkyl and sulfo and R _{79 is} α-bromoacryloylamino;

wherein

R _{76 has} the meanings given above;

c) 1: 2 metal complex dyes, such as the 1: 2 chromium complex dyes of the azo and azomethine dyes of the formula

wherein

R _{80 is} hydrogen, sulfo or phenylazo and R _{8 is} hydrogen or nitro, and the

Phenyl ring B ₁₀ can be substituted by halogen, CC ₄ alkyl and sulfo;

d) 1: 2 metal complex dyes, such as the symmetrical 1: 2 chromium complex dyes of the azo dyes of the formulas

wherein the phenyl ring bio can be substituted by halogen, CC ₄ -alkyl and sulfo and R ₈₂ and R ₈₃ independently of one another are hydrogen, nitro, sulfo, halogen, CC ₄ -alkylsulfonyl, dC ₄ - alkylaminosulfonyl and -S0 ₂ NH ₂ ;

wherein

R is hydrogen, dd-alkoxycarbonylamino, benzoylamino, C 1 -C ₄ -alkylsulfonylamino, phenylsulfonylamino, methylphenylsulfonylamino or halogen, hydrogen or halogen and R ₈₆ C _r C -alkylsulfonyl, CC ₄ -alkylaminosulfonyl, phenylazo, sulfo or - S0 ₂ NH _2, where the hydroxyl group in the benzene ring D ₁₀ in the o-position to the azo group is bonded to the benzene ring D _10;

symmetrical 1: 2 cobalt complexes of the azo dyes of the formulas

wherein

R _{87 is} the -OH or -NH ₂ group, R _{88 is} hydrogen or CC ₄ -alkylaminosulfonyl and R _{89 is} nitro or C _r C ₄ -alkoxy-C 1 -C 8 -alkylene aminosulfonyl,

asymmetrical 1: 2 chromium complex dyes of the azo dyes of the formulas

wherein one substituent R _{90 is} hydrogen and the other is sulfo;

wherein

R _{81 is} hydrogen or nitro, the phenyl rings B ₁₀ can be substituted by halogen, -CC ₄ -alkyl and sulfo and R _{85 is} hydrogen or halogen;

wherein the phenyl ring B _{10 can in} each case be substituted by halogen, CC ₄ alkyl and sulfo, R _{8 is} hydrogen or nitro, R _{91 is} hydrogen, methoxycarbonylamino or acetylamino and R ₈₆ CC ₄ alkylsulfonyl, C _r C ₄ alkylaminosulfonyl, phenylazo , Sulfo or -S0 ₂ NH ₂ ;

1: 2 chromium complex dyes of the azo dyes of the formulas (40) and (41);

1: 2 chromium mixed complexes of the azo dyes of the formulas (40) and (41);

the copper complex of the formula

wherein the benzene rings D ₂₀ are substituted by sulfo or sulfonamido;

e) Anthraquinone dyes of the formulas

wherein R _{79 is} α-bromoacryloylamino, R _{92 is} independently hydrogen or CC alkyl and R _{93 is} hydrogen or sulfo;

wherein the substituents < _M independently of one another mean cyclohexyl and the diphenyl ether radical, which can be substituted by sulfo and the radical -CH ₂ -NH-R ₇₉ , where R _{79 has} the meaning given; and

wherein

R _{79 is} cc-bromoacryloylamino, R _{92 has} the meanings given under formula (48) and R95 is C ₄ -C ₈ alkyl;

f) metal-free anionic anthraquinone dyes of the formulas (51) or (52)

wherein

(Rg6) ι- ₅ for 1 to 5 identical or different substituents selected from the group CC ₄ alkyl, which is optionally substituted by C ₂ -C ₄ alkanoylamino, which in turn can be substituted in the alkyl group by halogen, or benzoylamino ; d- C alkoxy; C ₂ -C ₄ alkanoylamino or C ₂ -C ₄ hydroxyalkylsulfamoyl; R _{97 is} CC ₄ alkyl, optionally substituted by CC ₄ alkyl, C ₅ -C ₇ cycloalkyl or phenyl optionally substituted by phenoxy, CC alkyl or sulfo, the phenoxy group in turn optionally being in the phenyl ring by CC ₄ alkyl, dC ₄ Alkoxy, halogen or sulfo, in particular CC ₄ alkyl or sulfo, is substituted; R ₉₈ and R ₉₉ are independently Cι-C ₄ alkyl, which is optionally substituted by C ₂ -C ₄ alkanoylamino which may itself be substituted in the alkyl group by halogen, or optionally in the phenyl ring by -C ₄ alkyl, Cι- C ₄ alkoxy, halogen or sulfo, in particular CC ₄ alkyl or sulfo, substituted phenoxy; or

g) monoazo dyes of the formulas (53), (54), (55), (56), (57) or (58)

wherein

/ 103

R _{100 is} halogen, trifluoromethyl or ^S0 2 ^N , where R _{103 is} cyclohexyl and R ₁₀₄

C 1 -C ₄ alkyl, or the radicals R ₁₀₃ and Rι ₀₄ together with the nitrogen atom connecting them form an azepinyl ring; R _{10 is} hydrogen or halogen and R _{102 is} hydrogen or phenoxy which is optionally substituted by halogen in the phenyl ring;

wherein

R _{105 is} hydrogen, halogen or sulfo; R ₁₀ e hydrogen, halogen, optionally in

Phenyl ring substituted by C _r C ₄ alkyl, CC alkoxy or halogen or phenoxy

Phenoxysulfonyl or a radical of the formula, wherein R ₁₁₀

phenyl which is optionally substituted by dC -alkyl, dC -alkoxy, halogen or sulfo, Rm is hydrogen or -CC -alkyl and X _{50 is} halogen; R _{107 is} hydroxy or amino; andRι ₀₈ and R _{109 are} independently hydrogen or halogen;

wherein

Rn ₂ and R ₁₁₃ independently of one another are hydrogen, CC ₄ alkyl, CC ₄ alkoxy, halogen or C -C ₄ alkanoylamino and preferably hydrogen or C 1 -C ₄ alkyl, R ₁₁ optionally by C _r C ₄ alkyl, CC ₄ alkoxy, halogen or C ₂ -C ₄ alkanoylamino substituted phenyl, preferably unsubstituted or substituted by CC ₄ alkyl, phenyl;

wherein

Rιι ₅ is hydrogen or alkyl dd, Rn ₆ is hydrogen or optionally in the phenyl ring by C -alkyl, C -C ₄ alkanoylamino substituted phenylsulfonyl, preferably unsubstituted phenylsulfonyl, ₄ alkoxy, halogen, or C _2;

wherein

R ₁₁₇ is hydrogen, C _r C ₄ -alkyl, C ₄ -alkoxy, halogen or optionally substituted in the phenyl ring by d-d alkyl, Cι-C ₄ alkoxy, sulfo, halogen or C ₂ -C ₄ alkanoylamino substituted phenoxy, preferably phenoxy which is unsubstituted or substituted by C 1 -C ₄ -alkyl or halogen, and

R ₁₁₈ optionally in the phenyl ring by C _r C ₄ -alkyl, C alkoxy, sulfo or halogen substituted benzoyl, preferably benzoyl unsubstituted or optionally substituted in the alkyl group by hydroxyl or Cι-C ₄ -alkoxy-substituted C ₂ -C ₄ - Alkanoyl and preferably unsubstituted C -C alkanoyl, such as acetyl; or

wherein

Rιι ₉ is hydrogen, CC ₄ alkyl, C _r C ₄ alkoxy, halogen or optionally in the alkyl group by hydroxy, Cι-C ₄ -alkoxy or halogen-substituted C ₂ -C ₄ alkanoylamino; R ₁₂₀ optionally substituted by -CC alkyl, -CC alkoxy, sulfo or halogen substituted phenyl, preferably unsubstituted phenyl, and

R _{121 is} hydrogen or CrC ₄ alkyl;

or disazo dyes of the formulas (59) or (60)

wherein

A ₂₀ and A _{2 are} residues of the formula (59a)

wherein

R ₁₀₇ , R ₁₀₈ and Rι ₀₉ independently of one another have the meanings given above; or

Suitable metal-free anionic acid dyes are, for example, dl. Acid Yellow 79, 110 and 246; dl. Acid Orange 67 and 94; dl. Acid Red 127, 131, 252 and 361; dl. Acid Green 40: 1 and dl. Acid Blue 225, 239, 260, 277 and 324 and especially the dyes of the formulas

99 66d3 / ± 3d 868SI / 00 OΛV

In the acid dyes of the formulas (34) to (59), the radicals R ₇₁ to R _{12 have} the following meanings:

Alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl or butyl, it being possible for the alkyl radicals to be further substituted, for example by hydroxyl, sulfo or sulfato; Alkoxy groups with 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, it being possible for the alkyl radicals to be further substituted, for example by hydroxyl, sulfo or sulfato; Halogen, such as fluorine, bromine or especially chlorine; -CC ₄ alkylsulfonyl such as methylsulfonyl and ethylsulfonyl; Cι-C ₄ alkylaminosulfonyl, such as methylaminosulfonyl and Ethylaminosulfonyl; dC ₄ alkoxycarbonylamino, such as methoxycarbonylamino and ethoxycarbonylamino; dC ₄ alkoxy -CC ₄ alkylene aminosulfonyl, such as methoxy ethylene aminosulfonyl; dC ₄ alkanoylamino such as propionylamino; C ₂ -C ₄ -hydroxyalkylsulfamoyl, such as β-hydroxyethylsulfamoyl; C ₅ -C ₇ cycloalkyl such as cyclopentyl and cyclohexyl.

The dyes of the formulas (61), (62), (63), (77) and (91) to (96) are of particular importance.

The acid dyes mentioned are known or can be obtained analogously to known production processes such as diazotization, coupling, addition and condensation reactions.

The dyes used in the inks, especially the reactive or acid dyes, should preferably be low in salt, i.e. a total salt content of less than 0.5 wt .-%, based on the weight of the dyes. Reactive or acid dyes which, due to their production and / or the subsequent addition of couping agents, have higher salt contents can e.g. desalted by membrane separation processes such as ultrafiltration, reverse osmosis or dialysis.

The inks preferably contain a total dye content of 0.01 to 35% by weight, in particular 0.05 to 30% by weight and preferably 0.1 to 20% by weight, based on the total weight of the ink.

Preferred inks for the process according to the invention are those which have a viscosity of 1 to 40 mPa-s (millipascal second), in particular 1 to 20 mPa-s and preferably 1 to 10 mPa-s. Inks with a viscosity of 2 to 6 mPa-s are of particular importance. Inks are also important which have a viscosity of 10 to 30 mPa-s.

The inks can contain thickeners of natural or synthetic origin, inter alia for the purpose of adjusting the viscosity. Examples of thickeners are commercially available alginate thickeners, starch ethers or locust bean ^•, in particular Nathumalginat alone or in admixture with modified cellulose, especially with preferably 20 to 25 weight percent Carboxymethyicellulose called. Examples of synthetic thickeners which may be mentioned are those based on poly (meth) acrylic acids or poly (meth) acrylamides.

The inks contain such thickeners e.g. in an amount of 0.01 to 2% by weight, in particular 0.01 to 1% by weight and preferably 0.01 to 0.5% by weight, based on the total weight of the ink.

The inks may also contain buffer substances, e.g. Borax, borate or citrate. Examples include borax, sodium borate, sodium tetraborate and sodium citrate. They are used in particular in amounts of 0.1 to 3% by weight, especially 0.1 to 1% by weight, based on the total weight of the ink, in order to maintain a pH of e.g. 4 to 10, preferably 5 to 8, set.

The inks may contain surfactants, redispersants or humectants as further additives.

The commercially available anionic or nonionic surfactants are suitable as surfactants. As a redispersant e.g. Mention betaine. A mixture of Na lactate (advantageously in the form of a 50 to 60% aqueous solution) and glycerol and / or propylene glycol in amounts of preferably 0.1 to 30% by weight, in particular 2 to 20% by weight, is preferred as the humectant. -%, used in the ink used in the invention.

If desired, the inks may also contain acid donors such as butyrolactone or sodium hydrogenphosphate, preservatives, fungi and / or bacterial growth inhibitors, foam-suppressing agents, sequestering agents, emulsifiers, water-insoluble solvents, oxidizing agents or deaerating agents.

Particularly suitable preservatives are formaldehyde-releasing agents, such as, for example, paraformaldehyde and trioxane, especially aqueous, about 30 to 40 percent by weight Formaldehyde solutions, as sequestering agents, for example sodium nitrilotriacetic acid, sodium ethylenediaminetetraacetic acid, especially sodium polymethaphosphate, especially sodium hexamethaphosphate, as emulsifiers, especially adducts of an alkylene oxide and a fatty alcohol, especially an adduct of oleyl alcohol and ethylene oxide, as water-insoluble solvents , saturated hydrocarbons, especially paraffins with a boiling range of about 160 to 210 ° C (so-called mineral spirits), as an oxidizing agent, for example an aromatic nitro compound, especially an aromatic mono- or dinitrocarboxylic acid or sulfonic acid, which is optionally present as an alkylene oxide adduct, in particular a nitrobenzenesulfonic acid and, for example, high-boiling solvents, especially turpentine oils, higher alcohols, preferably C ₈ -C ₁₀ -alcohols, terpene alcohols or deaerating agents based on mineral and / or silicone oils, in particular commercial formulations, as a deaerating agent Solutions from about 15 to 25 percent by weight of a mineral and silicone oil mixture and about 75 to 85 percent by weight of a C ₈ alcohol, such as 2-ethyl-n-hexanol. These are usually used in amounts of 0.01 to 5% by weight, in particular 0.01 to 5% by weight, based on the total weight of the ink.

The inks can also contain anionic copolymers, nonionic block copolymers or dispersants. This applies in particular to the inks containing at least one pigment or preferably at least one disperse dye.

As an anionic copolymer, copolymers based on acrylic acid, methacrylic acid or maleic acid are particularly suitable for the inks. Among these, preference is given to those which, by polymerization of acrylic and / or methacrylic acid and one or more copolymerizable monomers, are selected from the group consisting of maleic acid, N-vinylformamide, N-vinylacetamide, allylamine or diallylamine derivative, N-vinylpyrrolidone, N- Vinyl-N-methyl-formamide, N-vinyl-N-methyl-acetamide, N-vinyl

N-ethyl-acetamide, vinyl acetate, vinyl propionate, acrylonitrile, styrene, methacrylonitrile, acrylamide, methacrylamide and N-mono / NN-di-Cι-Cι ₀ -alkyl- (meth) acrylamide are available.

Anionic copolymers which are obtainable by copolymerization of acrylic or methacrylic acid and styrene are particularly preferred.

Acrylic and methacrylic acid-styrene copolymers with a molecular weight of 3000 to 16000, in particular 3000 to 10000, are very particularly preferred. Suitable nonionic block polymers for the inks are, in particular, alkylene oxide condensation products such as, for example, ethylene oxide adducts with polypropylene oxide (so-called EO-PO block polymers) and propylene oxide adducts with polyethylene oxide (so-called reverse EO-PO block polymers), and block polymers which are caused by the addition of styrene to polypropylene - And / or polyethylene oxide are available. Preference is given to ethylene-propylene oxide block polymers with molecular weights between 2,000 and 20,000, especially between 8,000 and 16,000, and an ethylene oxide content in the total molecule of 30 to 80%, in particular 60 to 80%.

Above all, anionic dispersants from the group of

(ba) acidic esters or their salts of alkylene oxide adducts of the formula

ft V-O— (-alkylene - 0 - ^ - χ

< ^γ ) _m where

X is the acid residue of an inorganic, oxygen-containing acid, such as sulfuric acid or preferably phosphoric acid, or else the residue of an organic acid, and Y is -C ₁₂ alkyl, aryl or aralkyl, "alkylene" represents the ethylene residue or propylene residue, and m are 1 to 4 and n are 4 to 50,

(bb) polystyrene sulfonates,

(bc) fatty acid taurides,

(bd) alkylated diphenyl oxide mono- or disulfonates,

(be) sulfonates of polycarboxylic acid esters,

(bf) with an organic dicarboxylic acid, or an inorganic polybasic acid converted adduct of 1 to 60, preferably 2 to 30, moles of ethylene oxide and / or propylene oxide onto fatty acids, fatty amides, fatty acids or fatty alcohols each having 8 to 22 carbon atoms or on trihydric to hexavalent alkanols having 3 to 6 carbon atoms,

(bg) lignin sulfonates, (bh) naphthalene sulfonates, and

(bi) formaldehyde condensation products.

The lignosulfonates (bg) used are primarily those ligninsulfonates or their alkali metal salts whose sulfo group content does not exceed 25% by weight. Lignin sulfonates containing 5 to 15% by weight of sulfo groups are preferred.

As formaldehyde condensation products (bi) there are e.g. Condensation products of liginsulfonates and / or phenol and formaldehyde, condensation products of formaldehyde with aromatic sulfonic acids, e.g. Condensation products of ditolyl ether sulfonates and formaldehyde, condensation products of naphthalenesulfonic acid with formaldehyde and / or naphthol or naphthylaminosulfonic acids with formaldehyde, condensation products of phenolsulfonic acids and / or sulfonated dihydroxydiphenyl sulfone and phenols or cresols with formaldehyde and / or disulfonic acid and derivative products with diphenylate and derivative urea into consideration.

Are preferred as (bi)

- condensation products of ditolyl ether sulfonates and formaldehyde as e.g. in US-A-4,386,037,

- Condensation products of phenol and formaldehyde with lignin sulfonates, such as those e.g. in US-A-3,931,072,

- Condensation products of naphthol (2) sulfonic acid 6, cresol, sodium bisulfite and formaldehyde [cf. FIAT Report 1013 (1946)], and

- condensation products from diphenyl derivatives and formaldehyde, as e.g. in US-A-4,202,838.

The compound of the formula is particularly preferred as (bi)

wherein

X the direct bond or oxygen,

A is the residue of an aromatic compound which is bonded to the methylene group by means of a ring carbon atom,

M hydrogen or a salt-forming cation, e.g. an alkali metal, alkaline earth metal or

Ammonium and n and p independently of one another represent a number from 1 to 4.

The compound of the formula is very particularly preferred as (bi)

wherein

(SO ^ a ^ means an average degree of sulfonation of 1 to 3.

The above dispersants are known or can be prepared analogously to known compounds by generally known processes.

The total content of anionic copolymer, nonionic block polymer and dispersant in the ink according to the invention is, for example, 3 to 9% by weight, based on the total weight of the ink. The ratio: anionic copolymer: nonionic block polymer dispersant in the finished ink can vary within a wide range, for example 1.5: 0.5: 1; 1: 0.5: 1.5; 1: 1: 1; 1: 0: 1; 1: 1: 0; 1: 0: 0; 0: 1: 1 or 0: 0: 1.

Inks are preferred which contain anionic copolymer and nonionic block polymer or anionic copolymer and dispersant or nonionic block polymer and dispersant.

Inks containing anionic copolymer, nonionic block polymer and dispersant are particularly preferred.

The inks preferably contain N-methyl-2-pyrrolidone, diethylene glycol, glycerol or in particular 1,2-propylene glycol, usually in an amount of 2 to 30% by weight, in particular 5 to 30% by weight and preferably 5 to 25% by weight .-%, based on the total weight of the ink.

Furthermore, the inks, in particular the inks containing reactive or acid dyes, can also contain solubilizers, such as e.g. ε-caprolactam.

The inks can be prepared in a conventional manner by mixing the individual components in the desired amount of water.

The method according to the invention for printing on textile fiber materials can be carried out with ink jet printers known per se and suitable for textile printing.

In the case of the inkjet printing process, individual drops of the ink are sprayed from a nozzle onto a substrate in a controlled manner. The continuous inkjet method and the drop on demand method are mainly used for this. In the case of the continuous ink-jet method, the drops are generated continuously, with drops not required for printing being discharged into a collecting container and recycled. In the case of the drop on demand method, however, drops are created and printed as desired; ie drops are only generated if this is necessary for printing. The drops can be generated, for example, by means of a piezo inkjet head, by means of thermal Energy (bubble jet) or using the continuous ink jet method. For the method according to the invention, preference is given to printing using a bubble jet or using a piezo inkjet head.

As textile fiber materials come in particular nitrogen-containing or hydroxyl-containing fiber materials, such as textile fiber materials made of cellulose, silk or in particular wool or synthetic polyamides.

Preferred fiber materials containing hydroxyl groups are fiber materials which consist entirely or partially of cellulose. Examples are natural fiber materials such as cotton, linen or hemp and regenerated fiber materials such as e.g. Viscose and lyocell. Viscose or preferably cotton are particularly preferred. The fiber materials mentioned are preferably in the form of flat textile fabrics, knitted fabrics or webs. These fiber materials are preferably printed with inks containing reactive dyes.

According to a preferred embodiment of the present invention, prior to printing with inks containing reactive dyes, the fiber material is pretreated, in which the fiber material to be printed is first treated with an aqueous alkaline liquor and the treated fiber material is optionally dried.

The aqueous alkaline liquor contains at least one of the usual bases which are used in conventional reactive printing processes for fixing the reactive dyes. The base is used, for example, in an amount of 10 to 100 g / l liquor, preferably 10 to 50 g / l liquor. Examples of suitable bases are sodium carbonate, sodium hydroxide, disodium phosphate, trisodium phosphate, sodium acetate, sodium propionate, sodium hydrogen carbonate, aqueous ammonia or alkali donors, such as sodium chloroacetate or sodium formate. Sodium hydrogen carbonate, sodium carbonate or a mixture of water glass and sodium carbonate is preferably used. The pH of the alkaline liquor is usually 7.5 to 13.5, preferably 8.5 to 12.5. In addition to the bases, the aqueous alkaline liquor can contain other additives, for example hydrotroping agents. Urea is preferably used as the hydrotroping agent, which is used, for example, in an amount of 25 to 200 g / l liquor, preferably 50 to 150 g / l liquor. The fiber material is preferably dried after the above pretreatment. However, the aqueous alkaline liquor can also be applied simultaneously or before or after printing with the ink containing the reactive dye.

After printing, the fiber material is advantageously dried, preferably at temperatures up to 150 ° C., in particular 80 to 120 ° C., and then subjected to a heat treatment process in order to complete the print or to fix the dye.

The heat treatment can e.g. be carried out by a warm dwell process, a thermal insulation process or preferably by a steaming process.

In the steaming process, the printed fiber material is e.g. a treatment in a steamer with possibly superheated steam, expediently at a temperature of 95 to 180 ° C., advantageously in saturated steam.

The printed fiber material is then usually washed out with water in the customary manner in order to remove unfixed dye.

Silk or silk-containing mixed fiber material are preferred as nitrogen-containing fiber materials. Not only the natural or cultivated silk (Mauibe silk, Bombyx ori) but also the various wild silk, especially Tussah silk, further Eri and Fagara silk, nest silk, Senagale silk, Mugase silk, as well as mussel and spider silk come into consideration as silk. Silk-containing fiber materials are in particular mixtures of silk with polyester fibers, acrylic fibers, cellulose fibers, polyamide fibers or wool. The textile material mentioned can be in a wide variety of processing forms, e.g. as fiber, yarn, woven or knitted fabric. These fiber materials are preferably printed with inks containing acid dyes.

A pre-treatment of the fiber material is preferably carried out for printing on silk or silk-containing fiber material. For this purpose, the fiber material is pretreated with an aqueous liquor containing a thickener and optionally a hydrotroping agent. Alginate thickeners, such as commercially available sodium alginate thickeners, are preferably used as thickeners, for example in an amount of 50 to 200 g / l liquor, preferably 100 to 200 g / l liquor can be used. The preferred hydrotrope used is urea, which is used, for example, in an amount of 25 to 200 g / l liquor, preferably 25 to 75 g / l liquor. The liquor can also contain other additives, such as ammonium tartrate. The liquor is preferably applied to the fiber material in accordance with the padding process, in particular with a liquor absorption of 70 to 100%. The fiber material is preferably dried after the above pretreatment.

According to the method according to the invention, natural or synthetic polyamide fiber materials can also be used. Wool is particularly suitable as a natural polyamide fiber material. As a synthetic polyamide fiber material e.g. Polyamide 6 and polyamide 66 fiber materials are considered.

After printing, the fiber material is optionally dried as described above and then subjected to a heat treatment process already described above in order to complete the print or to fix the dye.

Other fiber materials which may be mentioned are, for example, polyvinyl, polyacrylonitrile, polyamide, aramid, polypropylene, polyester or polyurethane. Polyester-containing fiber materials are preferred. Suitable polyester-containing fiber materials are those materials which consist entirely or partially of polyester. Examples are cellulose ester fibers, such as cellulose-2 ¹ /2-acetate fibers and triacetate fibers, and particularly linear polyester fibers, which are also optionally acid-modified, which are obtained, for example, by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis ( hydroxymethyl) -cyclohexane are obtained, as well as fibers from copolymers of terephthalic and isophthalic acid with ethylene glycol. Also suitable are polyester-containing mixed fiber materials, ie mixtures of polyester and other fibers. These fiber materials are preferably printed with inks containing dispersion dyes, in particular sublimable dispersion dyes. Of particular interest here are inks which contain disperse dyes of group b) given above.

After printing, the fiber material is dried at temperatures up to 150 ° C., preferably 80 ° to 120 ° C. The subsequent fixing of the fiber material takes place in the generally by dry heat (heat setting) or superheated steam under atmospheric pressure (HT fixation). The fixation can be carried out, for example, under the following conditions:

- Heat setting: 1 to 2 minutes at 190 to 230 ° C.

- HT fixation: 4 to 9 minutes at 170 to 190 ° C

Another printing process is transfer printing, which is suitable for the inks containing at least one disperse dye. In this case, the pressure is applied to an intermediate medium, from which the pressure is then transferred to the fiber material by heat.

As an intermediate medium e.g. Paper. Particularly suitable fiber materials are e.g. synthetic or regenerated fiber materials such as polyamide, polyester and polyacrylonitrile, especially polyester. The preferences given above apply to these fiber materials.

According to this method, the ink is applied to the intermediate medium, e.g. Paper, printed. Then it is preferably dried. Then the intermediate medium with the printed side is brought into contact with the fiber material, with or without mechanical pressure, and the transfer of the dye from the printed intermediate medium takes place by heating, e.g. to a temperature of 150 to 250 ° C, especially 170 to 210 ° C. If desired, the printed fiber material can be washed out in the usual way after the printing process.

For the inks and their additives, the preferences given above for the inks containing disperse dyes apply. The disperse dyes of group b) specified above are particularly suitable for this type of printing.

The inks containing a pigment are preferably applied to the fiber material together with a binder, it being possible for the ink to be applied simultaneously with the binder or before or after the binder. Examples of binders are acrylic polymers, such as, for example, poly (meth) acrylic esters, poly (meth) acrylamide, or the copolymers of (meth) acrylic esters or (meth) acrylamide with suitable comonomers, such as, for example, maleic, fumarate, itacon, mesacone -, citracon, vinyl vinegar, vinyloxy vinegar, vinyl propion , Croton-, Aconit-, Allylessig-, Allyloxyessig-, Allylmalon-, 2-Acrylamido-2-methylpropansul- ^" fon-, Glutacon- or Allylsuccinic acid or with esters of these acids, N-Vinylpyrrolidon, N- Vinylformamid, N-Vinylacetamid, (Meth) acrolein, N-vinyl-N-methylacetamide, vinylcaprolactam, styrene derivatives or vinylphosphonic acid; polyamide derivatives; synthetic resin dispersions; copolymers based on vinyl; diamide-aldehyde precondensates; copolymers containing N-vinyllactam or polymers based on butadiene Particularly suitable are the esters of the abovementioned acids with dC ₆ alcohols, such as, for example, methyl, ethyl, isopropyl or butyl alcohol.

Crosslinkers can also be used for printing with binders. These can be applied to the fiber material simultaneously with the binders or before or after the binders. Suitable crosslinkers are e.g. water-soluble melamine, formaldehyde-melamine and formaldehyde-urea resins or precondensates, such as trimethylolmelamine, hexamethylolmelamine or dimethylolurea or water-soluble formaldehyde (prec) condensation products with formamide, thiourea, guanidine, cyanamide, dicyandiamide and / or such as water-soluble organic sulfonates Sodium salt of naphthalene sulfonic acid, or glyoxal urea derivatives, e.g. the compound of formula

CH ~

\ ³

, ^N ~ H OH

0 = C I

^N _{N ^} CH OH

/ CH ₃

and especially N-methylol derivatives of nitrogen-containing compounds such as e.g. optionally etherified melamine / formaldehyde condensation products or N-methylol-urea compounds.

Examples of the optionally etherified melamine / formaldehyde condensation products are the compounds of the formulas

The optionally etherified N-methylol-urea compounds are e.g. for optionally subsequently etherified reaction products of formaldehyde with urea or urea derivatives, such as cyclic ethylene or propylene ureas, which may also contain substituents such as hydroxyl groups in the alkylene group, urones or optionally substituted triazone resins.

Examples of corresponding N-methylol-urea compounds are optionally modified N-methylol-hydroxyethylene urea products, e.g. the compounds of the formula

H ₃ COH ₂ C - NHCO - N - CH ₂ - C - CH (OH) - NHCONH - CH ₂ OCH ₃ , or Methylolierungspro- CH ₂ OH CH ₃

Products based on propylene urea or ethylene urea / melamine. Preferred crosslinkers are optionally modified N-methylol-hydroxyethylene urea compounds, methylolation products based on propylene urea or ethylene urea / melamine and in particular optionally etherified melamine / formaldehyde condensation products. Mixtures of two or more different water-soluble crosslinking agents can also be used, for example a mixture consisting of an unetherified and an only partially etherified melamine / formaldehyde condensation product. If desired, crosslinking catalysts can also be used. Suitable crosslinking catalysts for the process according to the invention are, for example, all agents which are customarily used as catalysts for crease and shrink-free finishing, as are known from the Textile Aids Catalog 1991, Konradin Verlag R. Kohlhammer, Leinfelden-Echterdingen 1991. Examples of suitable crosslinking catalysts are inorganic acids, for example phosphoric acid; Lewis acids, for example zinc chloride, zirconium oxychloride, NaBF ₄ , AICI ₃ , MgCl ₂ ; Ammonium salts, for example ammonium sulfate, ammonium chloride; or hydrohalides, in particular hydrochlorides of organic amines, for example CH ₃ -CH ₂ -CH ₂ -NH-CH ₃ . HCI. The use of ammonium salts or magnesium-containing Lewis acids and in particular ammonium chloride or magnesium chloride is preferred.

When printing on the fiber material, the pigment dye, the binder and optionally other auxiliaries, such as e.g. the crosslinker, applied to the fiber material. The binder and auxiliaries are generally applied in the form of aqueous preparations.

The heat treatment can be carried out by a warm dwell process, a thermal insulation process or preferably by a steaming process (HT fixation).

In the steaming process, the printed fiber material is subjected to a treatment in a steamer with possibly superheated steam, advantageously at a temperature of 95 to 210 ° C., advantageously 100 to 180 ° C.

The printed fiber material is preferably treated for 2 to 5 minutes at 150 to 170 ° C. during HT fixation.

The prints can be finished using the so-called thermal insulation process after or without intermediate drying, for example at a temperature of 100 to 210 ° C. The thermal insulation is preferably carried out at a temperature of 120 to 210 ° C., in particular the other 140 to 180 ° C. Depending on the temperature, the thermal insulation can take 20 seconds to 5 minutes, preferably 30 seconds to 4 minutes. The thermal insulation is usually carried out at 190 to 210 ° C. for 1 to 2 minutes.

After the printing process, the printed fiber material can be washed out in the usual way to remove unfixed dye. For this purpose, the fiber material is treated with water, for example at from 40 ° C. to boiling temperature, to which a soap or a synthetic detergent can optionally be added.

Ink-jet printing as well as subsequent drying and fixing can also be carried out in a single step. This means in particular that these steps are carried out continuously. That that devices for ink-jet printing, drying and fixing are installed one behind the other, through which the fiber material to be printed is continuously moved. The devices for ink-jet printing, drying and fixing can also be combined in a single machine. The fiber material is continuously transported through this machine and is then finished after leaving this machine. The drying can be e.g. by means of thermal energy (as indicated above, for example) or in particular by means of infrared radiation (IR). The fixation can be e.g. by means of ultraviolet radiation (UV) or by means of thermal energy (such as specified above). Of course, the ink-jet printing can also be done separately and drying and fixing are continuous, as indicated above, e.g. carried out in a single machine.

With the printing method according to the invention, it is possible to print the fiber materials both in a single color and in different colors. The printing method according to the invention is preferably carried out with at least two, preferably at least three and in particular at least four inks of different mixed colors. If the printing is done in a mixed color, the printing of the fiber material can be done over the whole area or with a pattern. The use of a single ink is naturally sufficient for this. If a print is to be made on the fiber material which has a plurality of mixed colors which are different from one another, then the fiber material is printed with a plurality of inks which each have the desired mixed color. According to the method according to the invention, each of the inks with which the corresponding mixed colors of a print are to be produced is produced separately, so that the digital color mixing of the basic colors on the fiber material, which is usually carried out in the inkjet printing process, is eliminated. The preparation can be carried out, for example, by dissolving the amount of at least two dyes of different colors, for example in a ratio of 1:99 to 99: 1, required for the desired mixed color in water with the addition of the auxiliaries customary for the respective inks. An ink formulation corresponding to a given color can be determined, for example, in accordance with the method specified in US Pat. No. 5,355,350. The inks for the process according to the invention can also be produced, for example, by mixing at least two, preferably at least three inks of different colors in the amount required for the desired mixed color, for example in a ratio of 1:99 to 99: 1.

In a particular embodiment of the method according to the invention, the desired mixed color is produced from the required amount of at least three dyes of different colors,

The process according to the invention has the advantage that any mixed color, even the finest nuances, can be produced on the fiber material, all mixed colors of the printed fabric, including the less intense and bright mixed colors, appearing bright and homogeneous to the viewer.

According to the invention, the less intensive and bright mixed colors are produced with inks which are further diluted before application in accordance with the desired shade. Suitable diluents are, for example, mixtures of water and at least one water-miscible organic solvent, such as N-methyl-2-pyrrolidone, diethylene glycol, glycerol, for example in an amount of 2 to 30% by weight, in particular 5 to 30 % By weight and preferably 5 to 25% by weight, based on the total weight of the diluent, are present. The solvent that is already contained in the undiluted ink is preferably selected as the component of the diluent. Furthermore, the method according to the invention has the advantage that the throughput, ie the area printed per unit of time, is higher than in the conventional inkjet printing method, since the generation of the mixed colors by the time-consuming digital color mixing on the fiber material to be printed is no longer necessary.

Another interesting embodiment relates to the so-called imaging. Here a color design to be printed is e.g. created on the computer with graphics software, which is then transferred to the fiber material using an ink-jet printer. The color design to be printed may e.g. also deal with letters, numbers, words, any pattern or even complex different colored images. Different colored images can e.g. by using multiple inks of different colors. The number of colors in a multi-color design is only limited by the technical possibilities of the inkjet printer used, i.e. by the number of inks that the inkjet printer used can print in one operation.

The prints obtainable by the process according to the invention have good general fastness properties; e.g. they have high fiber-dye binding stability in both the acidic and alkaline range, good lightfastness, good wet fastness properties such as water, wash, seawater, over-dyeing and perspiration fastness, good chlorine fastness, rubbing fastness, ironing fastness and pleating fastness and sharp contours and high color strength. The printing inks used are characterized by good stability and good viscosity properties.

The following examples serve to explain the invention. The temperatures are given in degrees Celsius, parts are parts by weight and the percentages relate to percentages by weight, unless stated otherwise. Parts by weight relate to parts by volume in the ratio of kilograms to liters.

Manufacturing Examples 1 to 46:

The following inks A, B, C and D are prepared by dissolving the specified reactive dyes in a mixture of 1, 2-propylene glycol and water in the specified proportions: Ink A: 10.0% by weight of the dye of the formula

20.0% by weight 1, 2-propylene glycol, 70.0% by weight water;

Ink B: 14.0% by weight of the dye of the formula

20.0% by weight 1, 2-propylene glycol, 66.0% by weight water;

Ink C: 10.0% by weight of the dye of the formula

20.0% by weight of 1,2-propylene glycol, 70.0% by weight water;

Ink D: 8.0% by weight of the dye of the formula

2.0% by weight of the dye of the formula

1: 2 Cr complex

20.0% by weight of 1,2-propylene glycol, 70.0% by weight of water.

The diluent E is prepared by mixing 20.0% by weight of 1,2-propylene glycol and 80.0% by weight of water.

The inks of the corresponding mixed colors are prepared from the inks A, B, C and D and, if appropriate, the diluent E by mixing the proportions given in Table 1: Table 1 :

Printing example 47: a) Mercerized cotton satin is padded with a liquor containing 40 g / l sodium carbonate and 100 g / l urea (liquor absorption 70%) and dried. b) The inks according to manufacturing examples 1, 2, 16 and 36 are printed on the pretreated cotton satin according to step a) using a commercially available inkjet printer in such a way that a color design results from these four mixed colors. The print is completely dried and fixed in saturated steam for 8 minutes at 102 ° C, rinsed cold, washed to the boil, rinsed again and dried. A print with good general fastnesses is obtained which appears homogeneous to the viewer from close up.

According to the procedure described in print example 47, multi-color designs can be printed on mercerized cotton satin if, instead of the inks used in print example 47 according to preparation examples 1, 2, 16 and 36, either one, two, three, four, five, six or seven different inks different mixed colors from Table 1 used. The number of mixed colors in a multi-color design is only limited by the technical possibilities of the inkjet printer used, ie by the number of inks that the inkjet printer used can print in one operation.

Manufacturing examples 48 to 93:

The following inks F, G, H and I are produced by dissolving the specified acid dyes in a mixture of 1, 2-propylene glycol and water in the specified proportions:

Ink F: 5.0% by weight of the dye of the formula

20.0% by weight 1,2 propylene glycol, 75.0% by weight water;

Ink G: 5.0% by weight of the dye of the formula

20.0% by weight of 1,2-propylene glycol, 75.0% by weight of water;

Ink H: 5.0% by weight of the dye of the formula

20.0% by weight 1,2 propylene glycol, 75.0% by weight water;

Ink I: 5.0% by weight of the dye of the formula

20.0% by weight 1, 2-propylene glycol, 75.0% by weight water.

The diluent J is prepared by mixing 20.0% by weight of 1,2-propylene glycol and 80.0% by weight of water.

The inks of the corresponding mixed colors are prepared from the inks F, G, H and I and, if appropriate, the diluent J by mixing the proportions given in Table 2: Table 2:

Print example 94: a) A silk fabric is padded with an aqueous liquor containing 270 g / l of a low molecular weight commercial alginate thickener, 150 g / l urea and 50 g / l of an aqueous ammonium tartrate solution (25% strength) and (liquor absorption 90%) and dried. b) The inks according to the preparation examples 48, 49, 63 and 83 are printed onto the silk fabric pretreated according to step a) using a commercially available inkjet printer in such a way that a color design results from these four mixed colors. The print is dried and fixed in saturated steam at 102 ° C and then washed out. A print with good general fastnesses is obtained which appears homogeneous to the viewer from close up.

According to the procedure described in print example 94, multi-color designs can be printed on silk fabric if one instead of that in print example 94 Inks used according to the preparation examples 48, 49, 63 and 83 either one, two, three, four, five, six or seven different inks of different mixed colors from Table 2 are used. The number of mixed colors in a multicolor design is only limited by the technical possibilities of the inkjet printer used, ie by the number of inks that the inkjet printer used can print in one operation.

Manufacturing examples 95 to 140:

The following inks K, L, M and N are prepared by dispersing the specified pigments in a mixture of diethylene glycol, glycerin and water in the specified proportions and adding a polyacrylate binder:

Ink K: 5.0% by weight of a pigment of the formula

10.0 wt .-% of a commercial, water present in dispersed form in polyacrylate binder (Carboset ^® 531), 15.0 wt .-% of diethylene glycol, 5.0 wt .-% glycerol, 65.0 wt .-% Water;

Ink L: 5.0% by weight of a pigment of the formula

Ink M: 5.0% by weight of a pigment of the formula

Ink N: 5.0% by weight of a pigment of the formula

10.0 wt .-% of a commercial, water present in dispersed form in polyacrylate binder (Carboset ^® 531), 15.0 wt .-% of diethylene glycol, 5.0 wt .-% glycerol, 65.0 wt .-% Water. The diluent O is obtained by mixing

15.0% by weight of diethylene glycol, 5.0% by weight of glycerin,

80.0 wt% water; manufactured.

The inks of the corresponding mixed colors are prepared from the inks K, L, M and N and, if appropriate, the diluent O by mixing the proportions given in Table 3:

Table 3:

Print example 141:

The inks according to the production examples 95, 96, 110 and 130 are printed onto a cotton fabric using a commercially available inkjet printer in such a way that a color design results from these four mixed colors. The print is dried completely and fixed at 190 ° C for 90 seconds. A print with good general fastnesses is obtained which appears homogeneous to the viewer from close up.

According to the procedure described in print example 141, multicolor designs can be printed on cotton fabric if instead of the inks used in print example 141 according to preparation examples 95, 96, 110 and 130, either one, two, three, four, five, six or seven different inks are used different mixed colors from Table 3 used. The number of mixed colors in a multi-color design is only limited by the technical possibilities of the inkjet printer used, i.e. by the number of inks that the inkjet printer used can print in one operation.

Manufacturing examples 142 to 187:

The following inks P, Q, R and S are each as shown in the following

Described, produced:

Ink P: 2.0% by weight of the disperse dye of the formula

be with

0.3% by weight of a dispersant based on a sulfonated condensation product composed of a mixture of chloromethyldiphenyl isomers and naphthalene and

3.0% by weight of an anionic copolymer of acrylic acid and styrene (Narlex ^® DX 2020 mixed and then ground in a wet mill to an average particle size of 0.2 to 1.0 μm. The mixture is then added with thorough stirring

1.0% by weight of a commercial surfactant,

3.7% by weight betaine monohydrate, 0.2% by weight of a commercially available preservative,

5.0% by weight glycerin (85%), 15.0% by weight diethylene glycol, 69.8% by weight water;

Ink Q: 3.0% by weight of a 1: 3 mixture of the disperse dyes of the formulas

(114) (1 15) become with

1.0% by weight of a dispersant based on a sulfonated condensation product of chloromethyldiphenyl isomer mixture and naphthalene and then mixed in a wet mill to an average particle size of 0.2 to 1.0 μm. Then the mixture is added with thorough stirring

3.0% by weight betaine monohydrate,

0.1% by weight of a commercially available preservative, 12.0% by weight glycerol (85%),

5.0% by weight diethylene glycol, 75.5% by weight water;

Ink R: 4.0% by weight of the disperse dye of the formula

be with

1.0% by weight of a dispersant based on a sulfonated condensation product of chloromethyldiphenyl isomer mixture and naphthalene and 3.0 parts by weight of an anionic copolymer based on a partially sulfated octylphenol ethoxylate with 25 ethylene oxide units per 1 mole of octylphenol (Emulphor ^® OPS 25) and then in a wet mill to an average particle size of 0.2 to 1.0 μm marry. Then the mixture is added with thorough stirring

1.7% by weight betaine monohydrate,

0.1% by weight of a commercially available preservative, 10.0% by weight glycerol (85%), 10.0% by weight diethylene glycol, 70.2% by weight water;

Ink S: 4.0% by weight of the disperse dye of the formula

be with

2.0% by weight of a dispersant based on a sulfonated condensation product composed of a mixture of chloromethyldiphenyl isomers and naphthalene and

1.0% by weight of a nonionic alkylene oxide block polymer (Pluronic ^® F108) and

8.0% by weight of an anionic copolymer of acrylic acid and styrene (Narlex ^® DX 2020) was mixed and then ground in a wet mill to an average particle size of 0.2 to 1.0 μm. Then the mixture is added with thorough stirring

2.0% by weight betaine monohydrate,

0.1% by weight of a commercially available preservative,

5.0% by weight glycerin (85%), 15.0% by weight diethylene glycol, 62.9% by weight water.

The diluent T is made by mixing 2.0% by weight of a dispersant based on a sulfonated condensation product composed of a mixture of chloromethyldiphenyl isomers and naphthalene,

2.0% by weight of betaine monohydrate, 10.0% by weight of glycerol (85%), 10.0% by weight of diethylene glycol, 76.0% by weight of water.

The inks of the corresponding mixed colors are prepared from the inks P, Q, R and S and, if appropriate, the diluent T by mixing the proportions given in Table 4:

Table 4:

Print example 188:

The inks according to the production examples 142, 143, 157 and 177 are printed on polyester fabric using a commercially available inkjet printer in such a way that a color design results from these four mixed colors. The print is dried and fixed in the superheated steam at 180 ° C for 8 minutes. A print with good general fastnesses is obtained which appears homogeneous to the viewer from close up.

According to the procedure described in print example 188, multicolor designs can be printed on mercerized cotton satin if, instead of the inks used in print example 188 according to preparation examples 142, 143, 157 and 177, either one, two, three, four, five, six or seven different inks of different mixed colors from Table 1 were used. The number of mixed colors in a multi-color design is only limited by the technical possibilities of the inkjet printer used, i.e. by the number of inks that the inkjet printer used can print in one operation.

Claims

claims

1. A method for printing on textile fiber materials according to the ink jet printing method, characterized in that each mixed color of a textile print is produced with an aqueous ink of the corresponding mixed color, the mixed color of the inks being obtained by mixing at least two reactive, acid, dispersion or Pigment dyes of different colors are set in the amount required for the desired mixed color.

2. The method according to claim 1, characterized in that the ink applied to the fiber material covers the surface of the fiber material in such a way that it migrates through the fiber material, so that the side of the fiber material facing away from the ink jet head is also colored.

3. The method according to one of claims 1 and 2, characterized in that the fiber material is printed with at least two, preferably at least three and in particular at least four inks of different mixed colors.

4. The method according to any one of claims 1 to 3, characterized in that light or less intense mixed colors of the inks are adjusted by dilution, a diluent being used for the dilution, which contains water and at least one water-miscible organic solvent.

5. The method according to any one of claims 1 to 4, characterized in that the ink has a viscosity of 1 to 40 mPa-s.

6. The method according to any one of claims 1 to 5, characterized in that an ink is used which has at least two reactive dyes of the formulas

A U (5)

and

contains what

Ai, A and A _{3 are} independently the remainder of a monoazo, disazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine dye; U is a reactive radical of the formula

-NH-CO-Y (1),

-S0 ₂ -Z (1a),

-W-alkylene- S0 ₂ -Z

(1b),

R

-W-alkylene - E alkylene '- S0 ₂ -Z (1c),

- alkylene - W - alkylene'— S0 ₂ -Z

(1d), R

-O-alkylene-W - alkylene'— S0 ₂ -Z

(1e) or R

-W - arylene- N - alkylene- -S0 ₂ -Z

(1f)

R ₁ R

means what

W is a group of the formula -SO ₂ -NR1-, -CONR _r or -NR _t CO-, Ri is hydrogen, unsubstituted or substituted by hydroxy, sulfo, sulfato, carboxy or cyano or dd-alkyl or a radical of the formula -alkylene - S0 ₂ -Z _

R

R is hydrogen, hydroxy, sulfo, sulfato, carboxy, cyano, halogen, CC ₄ -alkoxycarbonyl, dC -alkanoyloxy, carbamoyl or the group -S0 ₂ -Z,

Z is vinyl or a radical -CH ₂ -CH ₂ -U ₁ and d is a leaving group,

E is the radical -O- or -N (R ₂ ) -,

R _{2 is} hydrogen or CC ₄ alkyl, alkylene and alkylene 'independently of one another CC ₆ alkylene, and arylene an unsubstituted or by sulfo, carboxy, C 1 -C ₄ alkyl, C 1 -C ₄ alkoxy or

Halogen substituted phenylene or naphthylene radical means a heterocyclic reactive radical of the formula

_,. -N- -V

R ₃ N ^ ^ N (2)

X

is what

R _{3 is} hydrogen or unsubstituted or by carboxy, cyano, hydroxy, sulfo or

C-C alkyl substituted by sulfato,

X is a group which can be split off as an anion and

V is a group which can be split off as an anion, a non-reactive substituent or a radical of the formula

R

-N- alkylene S0 ₂ -Z (3a),

R, N alkylene - E - alkylene'- S0 ₂ -Z

(3b),

R,

- N- - arylene S0 ₂ -Z

(3c),

R,

- N - arylene - (alkylene) - W alkylene'- S0 ₂ -Z

(3d),

R ₃

-NN alkylene - S0 ₂ -Z (3e) or

- N-arylene-NH-CO-γ

(3f) R,

means what

R, R, R ₃ , E, W, Z, Y, alkylene, alkylene 'and arylene have the meanings given above and 1 is 0 or 1, or a heterocyclic reactive radical of the formula

means in which one of the radicals Xi is a group which can be split off as an anion and the other radical Xi is a non-reactive substituent, a radical of the formulas (3a) to (3f) or a group which can be split off as an anion, X _{2 is} a negative substituent and

R ₃ independently has the meaning given above; where the radicals Ai, A ₂ and A _{3 may} independently contain one or more further, identical or different reactive groups U;

R, R ₅ , β and R ₇ independently of one another are hydrogen or optionally substituted

Is -C ₄ alkyl;

Xi 'and X ₂ ' are halogen;

Bi is an aromatic or aliphatic bridge member or the rest of the formula

-N (R ₅ ) -BN (R ₆ ) - represents a piperazine residue.

7. The method according to any one of claims 1 to 5, characterized in that an ink is used which contains at least two disperse dyes of the formulas

wherein

R ₂₁ halogen, nitro or cyano,

R _{22 is} hydrogen, halogen, nitro or cyano,

R ₂₃ halogen or cyano,

R _{24 is} hydrogen, halogen, dd-alkyl or C _r C ₄ alkoxy,

R _{2 is} hydrogen, halogen or acylamino, and

R ₂₆ and R ₂ are independently allyl, dd-alkyl, which is unsubstituted or by

Hydroxy, acetoxy, -CC ₄ alkoxycarbonyl or phenoxy is substituted,

wherein

Phenylsulfoxy is optionally substituted by CC ₄ alkyl or CC ₄ alkyl sulfo, R ₂₉ amino or hydroxy,

R _{30 is} hydrogen or CC ₄ alkoxy,

R3 _{1 is} hydrogen or the radical -O-CeHs-SOs-NH-fCH _≥ ^ -O-dHs,

R _{32 is} hydrogen, hydroxy or nitro and

R _{33 is} hydrogen, hydroxy or nitro,

wherein

R ₄ CC ₄ alkyl which is unsubstituted or substituted by hydroxy,

R ₃₅ -CC ₄ alkyl,

R ₃₆ cyano,

R _{37 is} the rest of the formula - (CH ₂ ) 3-0- (CH ₂ ) ₂ -0-C ₆ H ₅ ,

R ₃₈ halogen, nitro or cyano, and

R _{39 is} hydrogen, halogen, nitro or cyano,

wherein

R ₀ -C ₄ -alkyl,

R ₄ ι C _r C alkyl which is unsubstituted or substituted by CC ₄ alkoxy and

R _{42 is} -COOCH ₂ CH ₂ OC ₆ H5 and R _{43 is} hydrogen or

R _{2 is} hydrogen and R ₃ -N = NC ₆ H ₅ are

where the rings A "and B" are unsubstituted or substituted one or more times with halogen,

wherein

R ₄₄ dC ₄ alkyl, which is unsubstituted or substituted by hydroxy, CC ₄ alkoxy or CC ₄ alkoxy -CC ₄ -alkoxy, and

contains.

8. The method according to any one of claims 1 to 5, characterized in that an ink is used which contains at least two disperse dyes of the formulas

wherein

R _{5 is} hydrogen or phenyl optionally substituted by C _r C ₄ alkyl, R _{46 is} hydroxy or amino optionally substituted by CC ₄ alkyl, and R _{7 is} hydrogen, CC ₄ alkoxy or phenoxy,

wherein

R ₄₈ and R _{49 are} -CC alkyl,

R ₅₀ halogen or -CC alkoxy, and

R _{5 is} hydrogen, nitro or halogen, and

contains.

9. The method according to any one of claims 1 to 5, characterized in that an ink is used which contains at least two pigment dyes of the formulas

wherein

R _{52 is} hydrogen, halogen, -CC alkyl, dd-alkoxy, nitro or cyano,

R _{53 is} hydrogen, halogen, nitro or cyano,

Rs * is hydrogen, halogen or phenylaminocarbonyl,

R _{55 is} hydrogen or hydroxy, and

R _{ς6 is} hydrogen or a radical of the formula - CONH- ^"R 59, where

R _{57 is} hydrogen, dd-alkyl or dC ₄ -alkoxy,

R _{58 is} hydrogen, CC ₄ alkoxy or halogen, and

R _{59 is} hydrogen, dC ₄ alkyl, dC alkoxy or halogen,

wherein

R ₆₀ and R _6i are independently CC alkyl and R ₆₂ and R _{63 are} halogen,

where the rings A, B, D and E are unsubstituted or mono- or polysubstituted by halogen,

wherein

R ₆ dd alkyi,

R _{65 is} hydrogen, halogen, dC ₄ alkyl, C 1 -C alkoxy, nitro or cyano,

R _{66 is} hydrogen, halogen, nitro or cyano,

R _{67 are} hydrogen, halogen, dd-alkyl, C _r C -alkoxy, nitro or cyano, and

wherein the rings A and B 'are unsubstituted or substituted one or more times with halogen.

10. The method according to any one of claims 1 to 5, characterized in that an ink is used which contains at least two of the following acid dyes:

a) Triphenylmethane dyes of the formula

wherein

R ₇₁ , R ₇₂ , R ₇₃ and R _{74 are} independently dC ₄ alkyl and R ₇₅ CC ₄ alkyl, CC ₄ alkoxy or hydrogen;

b) mono- and disazo dyes of the formulas

wherein

R _{76 is} benzoylamino, phenoxy, chlorophenoxy, dichlorophenoxy or methylphenoxy, R _{77 is} hydrogen, benzoyl, phenyl, dC ₄ alkyl, phenylsulfonyl, methylphenylsulfonyl, and the substituents R _{78 are} independently hydrogen or a phenylamino or N-phenyl-N-methylaminosulfonyl;

wherein the phenyl ring B, "can be substituted by halogen, CC.-alkyl and sulfo and R, _{9 is} α-bromoacryloylamino;

wherein

R _{76 has} the meanings given above;

: 2-chromium complex dyes of the azo and azomethine dyes of the formula c)

wherein

R _{80 is} hydrogen, sulfo or phenylazo and R _{81 is} hydrogen or nitro, and the phenyl ring B ₁₀ can be substituted by halogen, CC ₄ alkyl and sulfo;

d) symmetrical 1: 2 chromium complex dyes of the azo dyes of the formulas

wherein the phenyl ring B ₁₀ can be substituted by halogen, -CC-alkyl and sulfo and R ₈₂ and R ₈₃ independently of one another are hydrogen, nitro, sulfo, halogen, CC ₄ -alkylsulfonyl, CC ₄ - alkylaminosulfonyl and -S0 NH ₂ ;

wherein

_{R 4} are hydrogen, C ₄ alkoxycarbonylamino, benzoylamino, -C ₄ alkylsulfonylamino, phenylsulfonylamino, methylphenylsulfonylamino or halogen, R ₅ is hydrogen or halogen and R ₈₆ Cι-C alkylsulfonyl, CC ₄ alkylaminosulfonyl, phenylazo, sulfo or - S0 ₂ Is NH ₂ , the hydroxyl group in the benz ring D ₁₀ being bonded in the o-position to the azo group on the benz ring Dι ₀ ;

symmetrical 1: 2 cobalt complexes of the azo dyes of the formulas

wherein

R _{87 is} the -OH or -NH ₂ group, R _{88 is} hydrogen or C _r C ₄ -alkylaminosulfonyl and R _{89 is} nitro or -CC ₄ -alkoxy-dC -alkyleneaminosulfonyl,

asymmetrical 1: 2 chromium complex dyes of the azo dyes of the formulas

wherein one substituent R _{90 is} hydrogen and the other is sulfo;

wherein R _{81 is} hydrogen or nitro, the phenyl rings can be bio-substituted by halogen, dd-alkyl and sulfo and R _{85 is} hydrogen or halogen;

in which the phenyl ring B _{10 can in} each case be substituted by halogen, CC ₄ alkyl and sulfo, R _{8 is} hydrogen or nitro, R _{9 is} hydrogen, methoxycarbonylamino or acetylamino and R _{86 is} C 1 -C ₄ -alkylsulfonyl, CC ₄ -alkylaminosulfonyl, Is phenylazo, sulfo or -S0 ₂ NH ₂ ;

1: 2 chromium complex dyes of the azo dyes of the formulas (40) and (41);

1: 2 chromium mixed complexes of the azo dyes of the formulas (40) and (41);

the copper complex of the formula

wherein the benzene rings D ₂₀ are substituted by sulfo or sulfonamido;

e) Anthraquinone dyes of the formulas

wherein

R _{79 is} α-bromoacryloylamino, R _{92 is} independently hydrogen or CC ₄ alkyl and R _{93 is} hydrogen or sulfo;

wherein the substituents R ₉ independently of one another are cyclohexyl and the diphenyl ether radical, which can be substituted by sulfo and the radical -CH ₂ -NH-R ₇₉ , where R _{79 has} the meaning given; and

wherein

R _{79 is} α-bromoacryloylamino, R _{92 has} the meanings given under formula (48) and R _{95 is} dd-alkyl;

f) metal-free anionic anthraquinone dyes of the formulas (51) or (52)

wherein (R ₉ β) ι- ₅ for 1 to 5 identical or different substituents selected from the group C _r C ₄ alkyl, which is optionally substituted by C ₂ -C alkanoylamino, which in turn can be substituted in the alkyl group by halogen, or Benzoylamino is substituted; d- C alkoxy; C ₂ -C ₄ alkanoylamino or C ₂ -C ₄ hydroxyalkylsulfamoyl; R _{97 means} CC ₄ alkyl, optionally substituted by C _r C ₄ alkyl C ₅ -C ₇ cycloalkyl or phenyl optionally substituted by phenoxy, C 1 -C alkyl or sulfo, the phenoxy group in turn optionally in the phenyl ring by C 1 -C 4 -Alkyl, CC -alkoxy, halogen or sulfo, in particular CC ₄ -alkyl or sulfo, is substituted; R ₉₈ and R ₉₉ independently of one another CC ₄ alkyl, which is optionally substituted by C ₂ -C alkanoylamino, which in turn can be substituted in the alkyl group by halogen, or optionally in the phenyl ring by C 1 -C ₄ alkyl, dC ₄ alkoxy , Halogen or sulfo, in particular CC ₄ alkyl or sulfo, substituted phenoxy; or

g) monoazo dyes of the formulas (53), (54), (55), (56), (57) or (58)

wherein

/ "103

R _{100 is} halogen, trifluoromethyl or ^S0 2 ^N , where R _{103 is} cyclohexyl and Rι ₀₄

^R 10

C _{r is} C ₄ alkyl, or the radicals Rι ₀₃ and R ₁₀₄ together with the nitrogen atom connecting them form an azepinyl ring; R _{10 is} hydrogen or halogen and R _{02 is} hydrogen or phenoxy which is optionally substituted by halogen in the phenyl ring;

wherein

R _{105 is} hydrogen, halogen or sulfo; R ioβ hydrogen, halogen, optionally in

Phenyl ring by -CC alkyl, dC ₄ alkoxy or halogen substituted phenoxy or

Phenoxysulfonyl or a radical of the formula, wherein R ₁₁₀

phenyl optionally substituted by C 1 -C ₄ -alkyl, C _r C ₄ -alkoxy, halogen or sulfo, Rm is hydrogen or C _r C ₄ -alkyl and X _{50 is} halogen; R _{107 is} hydroxy or amino; andRι ₀₈ and R ₁₀ 9 are independently hydrogen or halogen;

wherein

R ₁₁₂ and R ₁₁₃ independently of one another are hydrogen, C 1 -C ₄ -alkyl, CC -alkoxy, halogen or dd-alkanoylamino and preferably hydrogen or dd-alkyl, Rn ₄ optionally by CC ₄ -alkyl, CC ₄ -alkoxy, halogen or C ₂ -C ₄ alkanoylamino is substituted phenyl, preferably phenyl which is unsubstituted or substituted by CC ₄ alkyl;

wherein

R _{115 is} hydrogen or dd-alkyl, Rn _{6 is} hydrogen or phenylsulfonyl, preferably unsubstituted phenylsulfonyl, preferably substituted by C _r C -alkyl, CC -alkoxy, halogen or C ₂ -C -alkanoylamino in the phenyl ring;

wherein

R ₁₁₇ is hydrogen, alkyl CC _4, CC ₄ -alkoxy, halogen or optionally substituted in the phenyl ring by Cι-C -alkyl, C ₄ alkoxy, sulfo, halogen or C ₂ -C ₄ alkanoylamino substituted

Phenoxy, preferably unsubstituted or substituted by C C alkyl or halogen

Phenoxy means and

Rιι ₈ optionally substituted in the phenyl ring by C _r C ₄ alkyl, C _r C ₄ alkoxy, sulfo or halogen benzoyl, preferably unsubstituted benzoyl, or optionally in the

Alkyl group substituted by hydroxy or -CC alkoxy C ₂ -C ₄ alkanoyl and preferably unsubstituted C ₂ -C ₄ alkanoyl, such as acetyl; or

wherein

R _{119 is} hydrogen, C 1 -C ₄ -alkyl, dC ₄ -alkoxy, halogen or C ₂ -C ₄ -alkanoylamino which is optionally substituted by hydroxy, C _r C ₄ -alkoxy or halogen in the alkyl group; R ₁₂ o optionally substituted by -CC ₄ alkyl, dC ₄ alkoxy, sulfo or halogen substituted phenyl, preferably unsubstituted phenyl, and

R _{121 is} hydrogen or -CC alkyl;

or disazo dyes of the formulas (59) or (60)

wherein

A ₂₀ and A _{2 are} residues of the formula (59a)

wherein

R ₁₀₇ , R ₁₀₈ and R ₁₀₉ independently of one another have the meanings given above; or

11. The method according to any one of claims 1 to 10, characterized in that an ink is used which has a total dye content of 0.01 to 35% by weight, in particular 0.05 to 30% by weight and preferably 0, 1 to 20 wt .-%, based on the total weight of the ink contains.

12. The method according to any one of claims 1 to 11, characterized in that an ink is used which has a viscosity of 2 to 6 mPa-s.

13. The method according to any one of claims 1 to 11, characterized in that an ink is used which has a viscosity of 10 to 30 mPa-s.

14. The method according to any one of claims 1 to 13, characterized in that drying and fixing of the print are carried out after the printing, the drying and fixing being carried out continuously.

15. The method according to claim 14, characterized in that the printing, drying and fixing of the print are carried out continuously.